Micellization-induced deprotonation of thermoresponsive surfactant CAE-85 — the telechelic carboxylic group derivative of Pluronic P85

Temperature-induced micellization of CAE-85, a carboxylic acid end-standing derivative of a triblock copolymer Pluronic P85, was studied by attenuated total reflectance Fourier-transform infrared spectroscopy (ATR FTIR) and density functional theory (DFT) model calculations. It was found that in polymer micelles carboxyl end groups dissociated and it was a two stage process. The first stage of deprotonation appeared with the onset of micellization and it was in agreement with predictions of existing models and theories for ionization processes in micellar corona. In micelles well above the critical micellization temperature, the degree of CAE-85 deprotonation increased further to values significantly higher compared to unimer solution. It is proposed that such deprotonation correlates with the formation of hydrogen bonded carboxyl end groups enabled by sufficient density of chains in the corona of developing micelles. It was demonstrated that the proton dissociation constant, pK_m, specific to the micellar form existed and was different from the proton dissociation constant of solution of unimers, pK_a.